CN108585544A - A method of base material is surface modified based on carbon nanotube assembling composite material - Google Patents
A method of base material is surface modified based on carbon nanotube assembling composite material Download PDFInfo
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- CN108585544A CN108585544A CN201810443889.9A CN201810443889A CN108585544A CN 108585544 A CN108585544 A CN 108585544A CN 201810443889 A CN201810443889 A CN 201810443889A CN 108585544 A CN108585544 A CN 108585544A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
- C09D177/04—Polyamides derived from alpha-amino carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention belongs to field of material engineering technology, disclose a kind of method being surface modified to base material based on carbon nanotube assembling composite material.By the way that base material is immersed in polyethylenimine solution, obtain positively charged substrate surface, then base material is immersed in successively in negatively charged modified carbon nano-tube dispersion liquid and said polycation solution, each 20min, conversion liquid, which is both needed to base material being put into pure water, every time cleans 2~3 times；Above-mentioned steps are recycled, it is the film modified base material of modified carbon nano-tube polyelectrolyte composite multi-layer to obtain surface.The present invention prepares the composite material of the carbon nano-tube modified polyelectrolyte of poly-dopamine by layer assembly, easy to operate, and without preparing special device, water can be used as solvent.This method can regulate and control the thickness of carbon nanotube composite multilayer membrane in nano-grade size, particularly suitable for the substrate material surface modification with irregular geometrical morphology, have larger application prospect.
Description
Technical field
The invention belongs to field of material engineering technology.Composite material is assembled based on carbon nanotube more particularly, to one kind
The method that base material is surface modified.
Background technology
Carbon nanotube（Carbon nanotubes, CNTs）As a kind of artificial carbon nanomaterial, from self-discovery just
It is widely paid close attention to because of its unique physicochemical properties.CNTs has excellent mechanical performance, good conductive heat transfer
Performance and extremely strong absorption property, while its chemical property is highly stable.These characteristics make CNTs multiple in electricity, optics and function
There is great application prospect in condensation material field.Simultaneously as CNTs has higher specific surface area and excellent electric property
And it is widely used in the different host material of surface modification, such as electrode, tissue engineering bracket, biosensor and implanted
Medical instrument etc..
But due to its bad dispersibility in water and organic solvent of CNTs, it is easy to reunite, it is difficult to prepare finely dispersed
Composite material greatly limits its application.The effects that physical or chemical modification is carried out to CNTs, is stacked using hydrophobic effect, π-π
So that surfactant cladding is wrapped in the tube wall of CNTs, to make it take charge, improves dispersibility.After functional modification
CNTs is positively charged or negative electrical charge, can carry out layer assembly with polyelectrolyte and prepare multilayer film, have very much in terms of surface modification
Application value.Layer-by-layer（Layer-by-Layer, LbL）, that is, the polyelectrolyte of opposite charges is carried in solid-liquid circle
Face forms the technology of multilayer film by alternating deposit.LBL self-assembly method have it is easy to operate, without preparing special device,
Water can be used as solvent.
Invention content
It is applied on surface-modified substrates material the technical problem to be solved by the present invention is to overcome the shortcomings of carbon nanotube,
Provide a kind of surface modification method assembling composite material based on carbon nanotube.
An object of the present disclosure is to provide a kind of carbon nanotube assembling composite material.
The second object of the present invention is to provide the carbon nanotube assembling composite material in substrate material surface modification
Using.
The third object of the present invention, which is to provide, is surface modified base material based on carbon nanotube assembling composite material
Method.
The above-mentioned purpose of the present invention is to give realization by the following technical programs：
A kind of assembling composite material based on carbon nanotube, be negatively charged modified carbon nano-tube is passed through with polycation it is quiet
Electro Sorb, layer assembly obtain modified carbon nano-tube-polyelectrolyte composite material.
Preferably, the negatively charged modified carbon nano-tube is dopamine auto polymerization modified carbon nano-tube；Utilize DOPA
Amine improves carbon nanotube hydrophilicity and assigns its negative electrical charge, due to quiet in carbon nano tube surface auto polymerization, forming layer poly-dopamine
Electric repulsive interaction improves carbon nanotube dispersibility.
Preferably, the polycation is poly-D-lysine or phthalic acid diethylene glycol diacrylate.
Preferably, the dopamine auto polymerization modified carbon nano-tube is that carbon nanotube is added in dopamine solution, room temperature
After ultrasound, stirring, standing.
It is highly preferred that a concentration of 0.01~1 mg/mL of dopamine solution, pH are 7.5~10.0.
It is highly preferred that the room temperature ultrasonic time is 0.3~2 h, mixing time is 10~48 h.
The auto polymerization that the present invention is occurred by dopamine under alkaline aerobic conditions first is reacted in carbon nano tube surface packet
A strata dopamine is covered, functional modification is carried out to it, and poly-dopamine modified carbon is further prepared by laminated assembling technology
Nanotube laminated electrostatic composite membrane（That is modified carbon nano-tube-polyelectrolyte composite material）, it can be achieved that carrying out table to base material
Face is modified.
Therefore, application of the above-mentioned assembling composite material based on carbon nanotube in substrate material surface modification is also in this hair
In bright protection domain；The base material is electrode, tissue engineering bracket, biosensor and implantable medical devices etc..
A method of base material is surface modified based on carbon nanotube assembling composite material, base material is soaked
Not in polyethylenimine solution, positively charged substrate surface is obtained, is then immersed in base material successively negatively charged
Modified carbon nano-tube dispersion liquid and said polycation solution in, each 20min, every time convert liquid be both needed to base material being put into it is pure
It is cleaned 2~3 times in water；Above-mentioned steps are recycled, it is modified carbon nano-tube-film modified base of polyelectrolyte composite multi-layer to obtain surface
Bottom material.
Preferably, the base material is platinum electrode or quartz plate；
Preferably, a concentration of 0.2~5 mg/mL of the polyethyleneimine, the soaking time of base material wherein be 5~
60min（It is preferred that 30min）.
Preferably, immersion of the base material in the modified carbon nano-tube dispersion liquid and said polycation solution of negative electrical charge
Time is 5~60min（It is preferred that 20min）；Soaking time is 1~20min in pure water（It is preferred that 2min）.
Preferably, a concentration of 0.2~1 mg/mL of the said polycation solution（It is preferred that 0.5mg/mL）；
It is highly preferred that the polycation is poly-D-lysine, phthalic acid diethylene glycol diacrylate or poly-（Two allyls
Base alkyl dimethyl ammonium chloride）.
Preferably, the modified carbon nano-tube of the negative electrical charge is dopamine auto polymerization modified carbon nano-tube；Specially by carbon
Nanotube is added in dopamine solution, after room temperature ultrasound, stirring, and standing.
It is highly preferred that a concentration of 0.01~1 mg/mL of dopamine solution, pH are 7.5~10.0.
It is highly preferred that the room temperature ultrasonic time is 0.3~2 h, mixing time is 10~48 h.
More specifically, for the dopamine of the MWCNTs of 0.2~3 mg/mL and 0.01~0.3 mg/ml are dissolved in 10
Mmol/L Tris-HCl（PH=8.5）In buffer solution, after 0.3~2h of room temperature ultrasound, 24~48h is stirred, is stood, stabilization is obtained
Poly-dopamine is carbon nano-tube modified（CNT@PDA）Dispersion liquid.
The present invention is also claimed assembles composite material modification by what any of the above-described method was prepared through carbon nanotube
Basis material.
Compared with prior art, the invention has the advantages that：
The present invention reacts carbon nano-tube modified by dopamine auto polymerization, under the premise of not changing carbon nanotube peculiar property,
The dispersibility of carbon nanotube is greatly improved, and there is higher stability；Layer assembly prepares poly-dopamine modified carbon
The composite material of nanotube-polyelectrolyte, this method is easy to operate, and without preparing special device, water can be used as solvent.It should
Method can regulate and control the thickness of carbon nanotube composite multilayer membrane in nano-grade size, particularly suitable for having irregular geometrical morphology
Substrate material surface modification.
Description of the drawings
Fig. 1 is poly-dopamine solution（It is left）, carbon nanotube（In）And the carbon nano-tube modified dispersion liquid of poly-dopamine（It is right）
Deployment conditions after standing 1 minute, 30 minutes and 30 days.Illustrate that dopamine auto polymerization is remarkably improved carbon nanotube in water
Dispersibility, and there is higher stability.
Fig. 2 is CNT@PDA/PDDA nano-multilayer film scanning electron microscope (SEM) photographs.The nanometer multilayer membrane structure is uniform.CNT@PDA：It is poly-
Dopamine is carbon nano-tube modified, PDDA：Phthalic acid diethylene glycol diacrylate.
Fig. 3 is that CNT PDA/PDDA nano-multilayer films modify platinum electrode scanning electron microscope (SEM) photograph.（A）Platinum electrode,（B）CNT@
PDA/PDDA nano-multilayer films modify platinum electrode,（C）Red frame portion position amplification in B figures,（D）As the CNT@PDA numbers of plies increase electricity
The charge transport capability of pole is stronger.
Specific implementation mode
It is further illustrated the present invention below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
It limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus routinely try for the art
Agent, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are purchased in market.
It is prepared by the carbon nano-tube modified dispersion liquid of 1 poly-dopamine of embodiment
The dopamine of the MWCNTs of 0.2~3 mg/mL and 0.01~0.3 mg/ml are dissolved in 10 Mmol/L Tris-HCl
（PH=8.5）In buffer solution, after 0.3~2h of room temperature ultrasound, 24~48h is stirred, stands, obtains stable poly-dopamine modified carbon
Nanotube（CNT@PDA）Dispersion liquid.Fig. 1 poly-dopamine solution（It is left）, carbon nanotube（In）And poly-dopamine modified carbon nanometer
Pipe dispersion liquid（It is right）Deployment conditions after standing 1 minute, 30 minutes and 30 days.Illustrate that dopamine auto polymerization is remarkably improved carbon and receives
The dispersibility of mitron in water, and there is higher stability.
The preparation of 2 PLL-CNT@PDA nano-multilayer films of embodiment
Clean quartz plate is immersed in 0.2~5 mg/ml polyetherimide（PEI）30 min in solution makes negatively charged
Quartz plate is combined under the action of electrostatic with positively charged PEI solution, activates quartz plate, its surface is made to form uniform unimolecule
Layer.Quartz plate is placed in ultra-pure water and is gently shaken, the PEI solution of quartz plate excess surface is washed away, then again by quartz plate according to
It is secondary to be immersed in the polylysin solution of CNT@PDA dispersion liquids and 0.5mg/ml, each 20min.Conversion liquid is both needed to stone every time
English piece, which is put into pure water, to be cleaned twice, every time 2 min.Solution all needs to change new soln after each use, to ensure solution
Stability.Above-mentioned steps are recycled, it is carbon nanotube layer and the PLL-CNT@altogether containing 10 layers of PDA layers of CNT@to finally obtain surface
PDA multilayer films.
The preparation of 3 PDDA-CNT@PDA nano-multilayer films of embodiment
By clean Pt（Platinum）Electrode（Fig. 3 A）It is immersed in 0.2~5 mg/ml polyetherimide（PEI）30 min in solution, makes
Negatively charged Pt electrodes are combined under the action of electrostatic with positively charged PEI solution, activate Pt electrodes, its surface is made to be formed
Even monolayer.Pt electrodes are placed in ultra-pure water and are gently shaken, wash away the extra PEI solution of Pt electrode surfaces, then again
Pt electrodes are immersed in the poly- of CNT@PDA dispersion liquids and 0.5mg/ml successively（Diallyldimethylammonium chloride）（PDDA）Solution
In, each 20min.Conversion liquid, which is both needed to Pt electrodes being put into pure water, every time cleans twice, every time 2 min.Solution makes every time
With new soln is all needed to change later, to ensure the stability of solution.Above-mentioned steps are recycled, it is carbon nanotube layer to finally obtain surface
And PDDA-CNT@PDA multilayer films containing 15 layers of PDA layers of CNT@altogether（Fig. 3 B and 3C）.The success of PDDA/CNT@PDA multilayer films
It is attached in platinum electrode, while increasing the charge transport capability of electrode, and as the CNT@PDA numbers of plies increase the electricity of electrode
Lotus transfer ability is stronger（Fig. 3 D）.
Claims (10)
1. a kind of assembling composite material based on carbon nanotube, which is characterized in that be by negatively charged modified carbon nano-tube with
Polycation obtains modified carbon nano-tube-polyelectrolyte composite material by Electrostatic Absorption, layer assembly.
2. the assembling composite material according to claim 1 based on carbon nanotube, which is characterized in that described negatively charged
Modified carbon nano-tube is dopamine auto polymerization modified carbon nano-tube.
3. the assembling composite material according to claim 1 based on carbon nanotube, which is characterized in that the polycation is
Poly-D-lysine or phthalic acid diethylene glycol diacrylate.
4. the assembling composite material according to claim 2 based on carbon nanotube, which is characterized in that the dopamine autohemagglutination
It is that carbon nanotube is added in alkaline dopamine solution to close modified carbon nano-tube, after room temperature ultrasound, stirring, and standing.
5. the assembling composite material according to claim 4 based on carbon nanotube, which is characterized in that the dopamine is molten
Liquid a concentration of 0.01~1 mg/mL, pH are 7.5~10.0.
6. the assembling composite material according to claim 4 based on carbon nanotube, which is characterized in that room temperature ultrasonic time
For 0.3~2 h, mixing time is 10~48 h.
7. any assembling composite material based on carbon nanotube of claim 1~6 is in substrate material surface modification
Using.
8. a kind of method being surface modified to base material based on carbon nanotube assembling composite material, which is characterized in that will
Base material is immersed in polyethylenimine solution, obtains positively charged substrate surface, then submerges base material successively
In negatively charged modified carbon nano-tube dispersion liquid and said polycation solution, each 20min converts liquid and is both needed to substrate every time
Material is put into pure water and cleans 2~3 times；Above-mentioned steps are recycled, it is modified carbon nano-tube-polyelectrolyte composite multi-layer to obtain surface
Film modified base material.
9. according to the method described in claim 8, it is characterized in that, a concentration of 0.2~5 mg/mL of the polyethyleneimine, base
The soaking time of bottom material wherein is 5~60min.
10. according to the method described in claim 8, it is characterized in that, the base material in modified carbon nano-tube dispersion liquid and
Soaking time in said polycation solution is 5~60min；Soaking time is 1~20min in pure water.
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Cited By (7)
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| CN109183277A (en) * | 2018-11-08 | 2019-01-11 | 上海师范大学 | A kind of conductive fiber flexible membrane and preparation method thereof |
| CN110027012A (en) * | 2019-05-10 | 2019-07-19 | 山东科技大学 | A kind of flexible pneumatic mechanical arm and preparation method thereof |
| CN110144762A (en) * | 2019-05-30 | 2019-08-20 | 方成 | A kind of preparation method of cellulose extrusion coating paper |
| CN110165230A (en) * | 2019-06-14 | 2019-08-23 | 齐鲁工业大学 | A method of bioelectrochemical system anode is prepared using carbon nanotube and carbon fiber |
| CN112326743A (en) * | 2020-11-05 | 2021-02-05 | 重庆医科大学 | C-SF-FA flexible conductive film based on silk fibroin, wearable wound monitoring sensor and preparation method of wearable wound monitoring sensor |
| CN113121859A (en) * | 2021-04-22 | 2021-07-16 | 哈尔滨工业大学 | Preparation method of electropolymerized polydopamine-carbon nanotube composite membrane |
| CN113529407A (en) * | 2021-07-13 | 2021-10-22 | 苏州大学 | Layer-by-layer self-assembly material, preparation method thereof and flexible strain sensor |
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Cited By (9)
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|---|---|---|---|---|
| CN109183277A (en) * | 2018-11-08 | 2019-01-11 | 上海师范大学 | A kind of conductive fiber flexible membrane and preparation method thereof |
| CN110027012A (en) * | 2019-05-10 | 2019-07-19 | 山东科技大学 | A kind of flexible pneumatic mechanical arm and preparation method thereof |
| CN110144762A (en) * | 2019-05-30 | 2019-08-20 | 方成 | A kind of preparation method of cellulose extrusion coating paper |
| CN110165230A (en) * | 2019-06-14 | 2019-08-23 | 齐鲁工业大学 | A method of bioelectrochemical system anode is prepared using carbon nanotube and carbon fiber |
| CN112326743A (en) * | 2020-11-05 | 2021-02-05 | 重庆医科大学 | C-SF-FA flexible conductive film based on silk fibroin, wearable wound monitoring sensor and preparation method of wearable wound monitoring sensor |
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| CN113121859A (en) * | 2021-04-22 | 2021-07-16 | 哈尔滨工业大学 | Preparation method of electropolymerized polydopamine-carbon nanotube composite membrane |
| CN113121859B (en) * | 2021-04-22 | 2022-09-02 | 哈尔滨工业大学 | Preparation method of electropolymerized polydopamine-carbon nanotube composite membrane |
| CN113529407A (en) * | 2021-07-13 | 2021-10-22 | 苏州大学 | Layer-by-layer self-assembly material, preparation method thereof and flexible strain sensor |
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